CN106040966A - Cold core box binder and casting molding body - Google Patents
Cold core box binder and casting molding body Download PDFInfo
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- CN106040966A CN106040966A CN201610206975.9A CN201610206975A CN106040966A CN 106040966 A CN106040966 A CN 106040966A CN 201610206975 A CN201610206975 A CN 201610206975A CN 106040966 A CN106040966 A CN 106040966A
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- component
- box binder
- resin
- phenolic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2273—Polyurethanes; Polyisocyanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C7/00—Patterns; Manufacture thereof so far as not provided for in other classes
- B22C7/06—Core boxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/542—Polycondensates of aldehydes with phenols
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mold Materials And Core Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a cold core box binder and a casting molding body and belongs to the technical field of binders. The cold core box binder comprises a first component. The first component is composed of, by weight, 40-80 parts of benzyl ether phenolic resin, 1-50 parts of high-boiling-point ester and/or hydrocarbon solvents and 0.1-10 parts of tackifying auxiliaries, wherein the content of hydroxymethyl of the benzyl ether phenolic resin is 32%-50%. According to the cold core box binder, the resin using amount is decreased to 0.55%-0.75% under the condition that the strength of a resin sand mold core is ensured; compared with the prior art, the resin using amount is greatly decreased, and the collapsibility of the resin sand mold core is greatly improved; and meanwhile, the residual quantity of tar on a metal mold is decreased, and the production efficiency is improved.
Description
Technical field
The present invention relates to adhesive techniques field, particularly relate to a kind of cold-box binder for non-ferrous casting resin sand
And casting body, this binding agent and casting aggregate mix cast mixture, and form manufacture casting under catalyst action
Make the core die of metal casting, be particularly suited for cast nonferrous alloy part.
Background technology
In foundary industry, existing cold-box binder is bi-component resin, different at triethylamine, dimethyl amine, dimethyl
Solidify under the catalytic action such as propylamine.Enough intensity is had, it is simple to delivery, carry and store, resin in order to ensure Resin-bonded sand mold and core
Addition is the highest, between 1.0-2.0%.When this binding agent is applied to cast iron or casting production, due to pouring temperature relatively
High (typically more than 1400 DEG C), binding agent can decomposes completely, sand core is easy to defeated and dispersed.
When existing cold-box binder is applied to non-ferrous casting, ensureing that Resin-bonded sand mold and core intensity meets the bar of serviceability
Under part, although resin amount is down to 0.85-1.2%, but owing to pouring temperature is relatively low (as aluminium alloy pouring temperature is 700-
800 DEG C), in sand core, binding agent is heated and decomposes the most completely, and resin sand can not be the most defeated and dispersed, causes knockout extremely difficult；Existing
Resin to also result in after cast residual tar amount on metal die higher, not only have impact on casting quality, and need when producing
Constantly the residual tar on cleaning mould, reduces production efficiency.
Many researchers is had to solve this problem, as United States Patent (USP) US4946876 discloses interpolation polyester attempting at present
Polyhydric alcohol improves the measure of collapsibility, but there is the shortcoming that sand core strength is low, exists simultaneously and improves asking of collapsibility the most completely
Topic；United States Patent (USP) US5132339 discloses interpolation Polyethylene Glycol (molecular weight 400) and improves the measure of collapsibility, but still exists
The shortcoming of moisture resistance difference, and collapsibility is not greatly improved；Chinese patent CN101524737A discloses employing binary
Primary resin system is carried out reactive modified by alcohol, improves the thermal decomposition performance of resin, solves core under relatively low pouring temperature and bursts
Dissipate sex chromosome mosaicism, but deposit after being cast on metal die residual tar amount high, affect casting quality, during production, still need to constantly clear up mould
Residual tar on tool, brings the shortcoming that production efficiency is low.
Chinese patent CN101147953 before applicant discloses a kind of high performance low smoke flame-proof amine method cold core box bonding
Agent, for Bicomponent binder, can improve the intensity of resin, improve the collapsibility problem of Resin-bonded sand mold and core the most completely.Cause
This, it is necessary on this basis, improve the collapsibility problem of Resin-bonded sand mold and core further, and while reducing residual tar amount
Meet intensity and the moisture resistance requirement of Resin-bonded sand mold and core.
Summary of the invention
The technical problem to be solved in the present invention is to provide one can ensure resin under conditions of Resin-bonded sand mold and core intensity
Usage amount is reduced to 0.55-0.75%, and compared with prior art, resin usage amount is substantially reduced, and improves bursting of Resin-bonded sand mold and core
Dissipate sex chromosome mosaicism, and in the cold-box bonding reducing the intensity meeting Resin-bonded sand mold and core while residual tar amount and moisture resistance requires
Agent and casting body.The present invention relates to a kind of cold-box binder, including component I, it is characterised in that described component I by with
The raw material composition of lower weight portion:
Benzylic ether phenolic resin 40～80 parts, preferably 50-70 part；
High boiling ester and/or hydrocarbon solvent 1～45 parts
Tackifying assistant 0～10 parts；
Wherein, the methylol group content of described benzylic ether phenolic resin is 32%～50% more than 27%.
Preferably, the methylol group content of described benzylic ether phenolic resin is 32%～50%.
Preferably, described cold-box binder also includes that component II, described component II are made up of the raw material of following weight portion:
Polyisocyanate 40～90 parts
High boiling ester and/or hydrocarbon solvent 5～45 parts
Tackifying assistant 0～10 parts.
Preferably, in described benzylic ether phenolic resin, the neighbour/contrast of functional group is more than 1；It is highly preferred that described benzylic ether phenol
Urea formaldehyde is that weight average molecular weight is at the high ortho position in 500～2000 benzylic ether phenolic resin；It is further preferred that described benzylic ether phenolic aldehyde
Resin is that molecular weight is at the high ortho position in 600～1200 benzylic ether phenolic resin.
Preferably, the high boiling ester in described component I and component II and/or hydrocarbon solvent are each independently selected from as adjacent benzene two
Formic acid dibutyl ester, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, adipic acid two are pungent
Fat, dimethyl succinate, Glutaric Acid Dimethyl ester, dimethyl adipate, methanol, ethanol, butanol, isopropanol, boiling range 150～290
DEG C petroleum liquid aromatic hydrocarbons fraction, one or more in kerosene；Wherein, described boiling range 150～the petroleum liquid virtue of 290 DEG C
Hydrocarbon fraction is solvesso 100, solvesso 150 or solvesso 200 one or more.
In most cases it is necessary to introduce solvent (diluent) in binding agent.The solvent that can use includes liquid
High boiling ester, vegetable oil, lower alcohol and hydro carbons, such as aromatic hydrocarbons.In the present invention, high boiling ester refers to that boiling point is at 100 400 DEG C
Between, especially between 150～400 DEG C, the particularly carboxylate between 200～400 DEG C, example includes phthalic acid
Dibutyl ester, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, adipic acid dibutyl ester, fourth
Acid dimethyl, Glutaric Acid Dimethyl ester, dimethyl adipate；The example of lower alcohol includes methanol, ethanol, butanol, isopropanol；Virtue
The example of hydrocarbon includes benzene,toluene,xylene and ethylbenzene and the petroleum liquid aromatic hydrocarbons fraction that boiling range is 150～290 DEG C；Excellent
Selection of land, the petroleum liquid aromatic hydrocarbons fraction of boiling range 150～290 DEG C is solvesso 100, solvesso 150, solvesso
One or more in 200.
Preferably, the tackifying assistant in described component I and component II is each independently selected from silane coupler, described silane
Coupling agent is one or more in A-187 silane, A-171 silane, A-172 silane, A-174 silane, A-151 silane.Preferably
Ground, the addition of above-mentioned tackifying assistant is 0.1～10 weight portions.Preferably, described high ortho position benzylic ether phenolic resin by with
Lower section method prepares:
Adding in reactor by aldehydes matter, aldehyde material, catalyst mixing, reaction prepares described phenolic resin；
The mol ratio of described aldehydes matter and aldehyde material is 1:1.0～1:3.0, preferably 1:1.2-1:2.5；
Catalyst is the catalyst system including slaine.
Preferably, described aldehydes matter is mixed phenol；It is furthermore preferred that described phenol mixture is in phenol, alkyl phenol
One or both combination；It is further preferred that described alkyl phenol is selected from 2,6-xylenol, orthoresol, metacresol, right
Cresol, 3,5-xylenol, 3,4-xylenol, 3-ethyl phenol, 3,5-diethyl phenol and the one or many to butylphenol
The combination planted.
Preferably, the catalyst system of slaine is included described in for comprising zinc salt and lead salt；Preferably, include described in
The catalyst system of slaine is for comprising zinc salt；It is furthermore preferred that described zinc salt is zinc acetate, zinc sulfate, zinc chloride, zinc naphthenate
In one or more.
Preferably, the polyisocyanate in described component II is selected from diphenyl methane-4,4 '-diisocyanate, thick hexichol
Methylmethane-4,4 '-diisocyanate or polymethylene polyphenyl polyisocyanates, hexamethylene diisocyanate, isophorone two
One or more in isocyanates.The polyisocyanate that the present invention uses can be aliphatic polymeric isocyanate or fragrance adoption
Isocyanates, the example of aliphatic polymeric isocyanate has isophorone diisocyanate, hexamethylene diisocyanate.Aromatic series
The example of polyisocyanate has diphenyl methane-4,4 '-diisocyanate (referred to as " MDI "), thick diphenyl methane-4,4 '-
Diisocyanate (referred to as thick " MDI ") or poly methylene poly phenyl poly isocyanate (referred to as " PAPI "), or their group
Compound.Each component of said components I and component II can be single component, or mixes with the component other described,
Owing to benzylic ether resin can react with polyisocyanate and solidify, typically carry out when Foundry Production mixing and preparing casting
Body.
By selecting this specific benzylic ether phenolic resin, the viscosity of binding agent can be reduced so that be mixed with binding agent
Casting model powder there is higher free-running property and higher sand mould intensity.High ortho position benzylic ether phenolic aldehyde is preferably used in the present invention
Resin, so-called high ortho position benzylic ether phenolic resin refers to the neighbour/contrast phenolic resin more than 1, and major part is ortho position in other words
Phenolic resin.Use high ortho position benzylic ether phenolic resin can obtain curing rate faster.
In order to prepare the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content, can prepare by the following method:
Step 1: the phenol melted, bisphenol-A, paraformaldehyde, calcium oxide, zinc acetate are put in reactor and stir all
Even, lower ph value of mixture 4～7 with PH regulator at 30～40 DEG C；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, then evacuation, make vacuum reach 300mmHg～
600mmHg, evacuation 25～i.e. obtain high ortho position benzylic ether phenolic resin for 35 minutes.
It will be appreciated by those skilled in the art that above-mentioned preparation method is not uniquely to prepare the high ortho position benzyl of high hydroxyl content
The method of ether phenolic resin, by adjusting the content of each component, or changes akin raw material, or carries out reaction condition
Adjustment can prepare the high ortho position benzylic ether phenolic resin of correspondingly high methylol group content.
Wherein, alkyl phenol replaces bisphenol-A can also obtain the high ortho position benzylic ether phenolic resin of high methylol group content, alkyl
What phenol can use has 2,6-xylenol, orthoresol, metacresol, paracresol, 3,5-xylenol, 3,4-dimethyl benzene
Phenol, 3-ethyl phenol, 3,5-diethyl phenol and to butylphenol etc..
By calcium oxide and zinc acetate as composite catalyst, it is possible to obtain the high ortho position benzylic ether phenol of high methylol group content
Urea formaldehyde.Some of them bivalent metal oxide including barium, magnesium oxide etc. can be replaced calcium oxide and reach goal of the invention, with
The zinc salts such as the zinc sulfate of zinc ion, zinc chloride, zinc naphthenate can also be replaced zinc acetate and reach goal of the invention, need explanation
It is that single zinc salt catalyst is the most helpful to the high ortho position benzylic ether phenolic resin obtaining higher methylol group content.
On the other hand, the present invention relates to a kind of casting body, it is characterised in that by casting aggregate and the right of effective dose
Prepare under catalyst action after requiring the arbitrary described cold-box binder mixing of 3-9-8；Wherein, by described cold-box
Described component I of binding agent and component II are sequentially added into, or are simultaneously introduced and mix with described casting aggregate.
Preferably, described cold-box binder is mixed with described casting aggregate by the weight ratio of 0.55%～0.75%.
By methods known in the art, different types of aggregate and different amounts of binding agent are used for preparation casting mixing
Thing.Use this adhesive system and suitable aggregate can prepare common molded body, hot investment casting molded body, non-ferrous casting molding
Body, is especially suitable for preparing non-ferrous casting molded body.The amount of binding agent used and the type of aggregate for those skilled in the art are
Known.The aggregate being preferred for preparing cast mixture is sand, the sand of wherein at least about 70wt%, preferably at least about 85wt%
For Silicon stone.Other aggregate materials for conventional cast molded body being suitable for include zircon, olivine, aluminosilicate, chromite
Sand etc..
Those skilled in the art are it should be apparent that can add other additives such as siloxanes, take off in aggregate or cast mixture
Mould agent, defoamer, wetting agent etc..The specific purposes of designer are depended in the selection of special additive.
Cold-box binder is in non-ferrous casting is applied, and on the basis of the weight of aggregate, the amount of cold-box binder is usual
It is not more than 2wt%, and usually in the range of 0.85-1.2wt%.
In order to improve casting body collapsibility in casting process, and meet while reducing residual tar content
The requirement of strength of Resin-bonded sand mold and core, it is preferable that described cold-box binder presses the weight ratio of 0.55%～0.75% and described casting
Make aggregate mixing.
It is further preferred that the catalyst preparing casting body is gaseous state amine, gaseous state amine can be triethylamine, dimethyl
Ethamine or dimethylisopropylamine, preferably triethylamine.
The present invention, by optimizing the preparation technology of high ortho position benzylic ether phenolic resin further, uses composite catalyst
(calcium oxide and zinc acetate) is prepared for the high ortho position benzylic ether phenolic resin of high methylol group content, high ortho position benzylic ether phenolic resin
The methylol of high-load can solidify with the isocyano fast reaction of isocyanates, thus increase substantially resin glue
Room temperature performance, on the one hand makes the resin sand normal temperature strength prepared be greatly improved；On the other hand the use of resin glue
Measure also to have and significantly decline so that Resin-bonded sand mold and core collapsibility in casting process is improved, and remains in metal after cast
Tar content on mould is also greatly reduced, and makes production efficiency be largely increased.
In sum, beneficial effects of the present invention shows themselves in that
1) cold-box binder of the present invention, by high ortho position benzylic ether phenolic resin and the Carbimide. of high methylol group content
The fast setting reaction of resin improves the normal temperature strength of resin glue, so that the content of resin glue is greatly reduced,
Improve the collapsibility of Resin-bonded sand mold and core in casting process, reduce the tar content on metal die, and improve prepared
The normal temperature strength of resin sand, substantially increase production efficiency；
2) present invention cold-box binder, be prepared into by the composite catalyst technology using calcium oxide and zinc acetate
Arrive the high ortho position benzylic ether phenolic resin of high hydroxyl content, improve the reactivity with isocyanate resin；
3) cold-box binder of the present invention, when being applied to non-ferrous casting, can reduce usage amount, reduce and produce into
This, improve production efficiency, can be widely popularized and use.
Detailed description of the invention
For making embodiments of the invention solve the technical problem that, technical scheme and advantage clearer, below in conjunction with
Specific embodiment is described in detail.But the present invention is limited to absolutely not these examples.The following stated is only the present invention and preferably implements
Example, only in order to explain the present invention, therefore can not be interpreted as the restriction of the scope of the claims of the present invention.It should be pointed out that, it is all
Any amendment, equivalent and the improvement etc. made within the spirit and principles in the present invention, should be included in the guarantor of the present invention
Within the scope of protecting.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Being measured the methylol group content of high ortho position benzylic ether phenolic resin, assay method is with reference to GB/T14074-
2006, to characterize the impact on resin sand intensity of its methylol group content.
Embodiment one
Cold-box binder:
The preparation of component I: equipped with in the mixing kettle of agitator, add the high ortho position benzylic ether phenolic aldehyde of high methylol group content
Resin 586 kilograms, adipic acid dibutyl ester 206 kilograms, 199 kilograms of Solvesso 150 aromatic hydrocarbons, 9 kilograms of A-187 silane, starts and stirs
Mix, mix about 2 hours, make material mix homogeneously.Wherein, the methylol group content of high ortho position benzylic ether phenolic resin is 32.99%,
Weight average molecular weight is 1000.
The preparation of component II: equipped with in the mixing kettle of agitator, add diphenyl methane-4,4 '-diisocyanate 800
Kilogram, dioctyl phthalate 173 kilograms, 18 kilograms of Solvesso 150 aromatic hydrocarbons, 9 kilograms of A-187 silane, start stirring,
Mix about 2 hours, make material mix homogeneously.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain the cold-box binder of the present invention.
The cold-box binder of the present invention can be mixed with sand by the weight ratio of 0.55%～0.75% be applied to coloured
Casting, obtains non-ferrous casting molded body.
Wherein, the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content is referred to following methods and prepares:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 312 kilograms, calcium oxide 4 kilograms,
Stirring in 0.6 kilogram of input reactor of zinc acetate, lowering ph value of mixture with PH regulator at 30～40 DEG C is 4～7；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, and then evacuation makes vacuum reach 300mmHg, takes out true
The empty high ortho position benzylic ether phenolic resin i.e. obtaining high methylol group content for 30 minutes.
Comparative example one
Cold-box binder:
The preparation of component I: identical with embodiment one, the hydroxyl first of the high ortho position benzylic ether phenolic resin except for the difference that added
Base content is 25.38%.
The preparation of component II is with embodiment one.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain cold-box binder.
Wherein, above-mentioned high ortho position benzylic ether phenolic resin can be prepared by the following method:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 312 kilograms, calcium oxide 4.6 thousand
Stirring in gram input reactor, lowering ph value of mixture with PH regulator at 30～40 DEG C is 4～7；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, and then evacuation makes vacuum reach 300mmHg, takes out true
Sky i.e. obtains high ortho position benzylic ether phenolic resin for 30 minutes.
Embodiment two
Cold-box binder:
The preparation of component I: equipped with in the mixing kettle of agitator, add the high ortho position benzylic ether phenolic aldehyde tree of high hydroxyl content
400 kilograms of fat, dibutyl phthalate 313 kilograms, 187 kilograms of Solvesso 150 aromatic hydrocarbons, A-187 silane double centner, open
Dynamic stirring, mixes about 2 hours, makes material mix homogeneously.Wherein, the methylol group content of high ortho position benzylic ether phenolic resin is
39.30%, weight average molecular weight is 600.
The preparation of component II: equipped with in the mixing kettle of agitator, add diphenyl methane-4,4 '-diisocyanate 800
Kilogram, dibutyl phthalate 163 kilograms, ethanol 10 kilograms, 18 kilograms of Solvesso 200 aromatic hydrocarbons, A-174 silane 9,000
Gram, start stirring, mix about 2 hours, make material mix homogeneously.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain the cold-box binder of the present invention.
The cold-box binder of the present invention can be mixed with sand by the weight ratio of 0.55%～0.75% be applied to coloured
Casting, obtains non-ferrous casting molded body.
Wherein, the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content is referred to following methods and prepares:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 398 kilograms, calcium oxide 4 kilograms,
Stirring in 1 kilogram of input reactor of zinc acetate, lowering ph value of mixture with PH regulator at 30～40 DEG C is 5～6；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, and then evacuation makes vacuum reach 600mmHg, takes out true
The empty high ortho position benzylic ether phenolic resin i.e. obtaining high methylol group content for 25 minutes.
Comparative example two
Cold-box binder:
The preparation of component I: identical with embodiment two, the hydroxyl first of the high ortho position benzylic ether phenolic resin except for the difference that added
Base content is 22.69%.
The preparation of component II is with embodiment two.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain cold-box binder.
The preparation method of above-mentioned high ortho position benzylic ether phenolic resin refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 275 kilograms, zinc acetate 4.6 thousand
Stirring in gram input reactor, lowering mixed liquors with PH regulator at 30～40 DEG C is 4～7；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, and then evacuation makes vacuum reach 600mmHg, takes out true
Sky i.e. obtains high ortho position benzylic ether phenolic resin for 25 minutes.
Embodiment three
Cold-box binder:
The preparation of component I: equipped with in the mixing kettle of agitator, add the high ortho position benzylic ether phenolic aldehyde of high methylol group content
Resin 634 kilograms, dioctyl phthalate 245 kilograms, 110 kilograms of Solvesso 150 aromatic hydrocarbons, 11 kilograms of A-187 silane,
Start stirring, mix about 2 hours, make material mix homogeneously.Wherein, the methylol group content of high ortho position benzylic ether phenolic resin is
35.69%, weight average molecular weight is 800.
The preparation of component II: equipped with in the mixing kettle of agitator, add polymethylene polyphenyl polyisocyanates 700,000
Gram, dioctyl phthalate 111 kilograms, 180 kilograms of Solvesso 100 aromatic hydrocarbons, 9 kilograms of A-187 silane, start stirring, mixed
About 2 hours, make material mix homogeneously.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain the cold-box binder of the present invention.
The cold-box binder of the present invention can be mixed with sand by the weight ratio of 0.55%～0.75% be applied to coloured
Casting, obtains non-ferrous casting molded body.
The preparation method of the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 368 kilograms, calcium oxide 4 kilograms,
Stirring in 1 kilogram of input reactor of zinc acetate, lowering mixed liquor with PH regulator at 30～40 DEG C is 5～6；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, and then evacuation makes vacuum reach 400mmHg, takes out true
The empty high ortho position benzylic ether phenolic resin i.e. obtaining high methylol group content for 30 minutes.
Comparative example three
Cold-box binder:
The preparation of component I: identical with embodiment three, the hydroxyl first of the high ortho position benzylic ether phenolic resin except for the difference that added
Base content is 16.78%.
The preparation of component II is with embodiment three.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain cold-box binder.
The preparation method of above-mentioned high ortho position benzylic ether phenolic resin refers to:
Step 1: will stir in the phenol 420 kilograms melted, paraformaldehyde 208 kilograms, 6 kilograms of input reactors of calcium oxide
Mixing uniformly, lowering mixed liquor with PH regulator at 30～40 DEG C is 5～6；
Step 2: reactor condenser is adjusted to reflux state, under agitation heats up, made temperature rise in 60 minutes
95 DEG C, and 95～105 DEG C of insulation reaction 90 minutes；
Step 3: reactor is adjusted to normal pressure fractional distillation state, made temperature in the kettle rise to 115 DEG C in 60 minutes, and
115～120 DEG C of insulation reaction 60 minutes；
Step 4: be incubated complete, cools to less than 100 DEG C, and then evacuation makes vacuum reach 400mmHg, takes out true
Sky i.e. obtains high ortho position benzylic ether phenolic resin for 30 minutes.
Embodiment four
Cold-box binder:
The preparation of component I: equipped with in the mixing kettle of agitator, add the high ortho position benzylic ether phenolic aldehyde of high methylol group content
Resin 700 kilograms, dimethyl adipate 291 kilograms, 9 kilograms of A-187 silane, starts stirring, mixes about 2 hours, make material mix
Close uniformly.Wherein, the methylol group content of high ortho position benzylic ether phenolic resin is 33.42%, and weight average molecular weight is 1200.
The preparation of component II: equipped with in the mixing kettle of agitator, adds 1, hexamethylene-diisocyanate 800 kilograms, adjacent benzene
Dioctyl phthalate dioctyl ester 141 kilograms, 150 kilograms of Solvesso 100 aromatic hydrocarbons, 9 kilograms of A-187 silane, start stirring, mixing about 2 is little
Time, make material mix homogeneously.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain the cold-box binder of the present invention.
The cold-box binder of the present invention can be mixed with sand by the weight ratio of 0.55%～0.75% and carry out coloured casting
Make, obtain non-ferrous casting molded body.
The preparation method of the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 348 kilograms, calcium oxide 5 kilograms,
Stirring in 0.8 kilogram of input reactor of zinc acetate, lowering mixed liquor with PH regulator at 30～40 DEG C is 5～6；
Step 2～4: reference example one preparation method step 2～4.
Comparative example four
Cold-box binder:
The preparation of component I: identical with embodiment four, the hydroxyl first of the high ortho position benzylic ether phenolic resin except for the difference that added
Base content is 19.32%.
The preparation of component II is with embodiment four.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain cold-box binder.
The preparation method of above-mentioned high ortho position benzylic ether phenolic resin refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 258 kilograms, sodium hydroxide 5,000
Stirring in gram input reactor, lowering mixed liquors with PH regulator at 30～40 DEG C is 8～10；
Step 2～4: with reference to comparative example two preparation method step 2～4.
Embodiment five
Cold-box binder:
The preparation of component I: equipped with in the mixing kettle of agitator, add the high ortho position benzylic ether phenolic aldehyde of high methylol group content
Resin 850 kilograms, dibutyl phthalate 35 kilograms, dimethyl adipate 6 kilograms, 25 kilograms of Solvesso 100 aromatic hydrocarbons,
75 kilograms of Solvesso 100 aromatic hydrocarbons, 9 kilograms of A-187 silane, starts stirring, mixes about 2 hours, make material mix homogeneously.Its
In, the methylol group content of high ortho position benzylic ether phenolic resin is 27.62%, and weight average molecular weight is 1800.
The preparation of component II: equipped with in the mixing kettle of agitator, adds 1, hexamethylene-diisocyanate 700 kilograms,
281 kilograms of Solvesso 100 aromatic hydrocarbons, 10 kilograms of butanol, 9 kilograms of A-174 silane, starts stirring, mixes about 2 hours, make material
Mix homogeneously.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain the cold-box binder of the present invention.
The cold-box binder of the present invention can be mixed with sand by the weight ratio of 0.55%～0.75% be applied to coloured
Casting, obtains non-ferrous casting molded body.
The preparation method of the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 80 kilograms, paraformaldehyde 372 kilograms, calcium oxide 3 kilograms,
Stirring in 0.1 kilogram of input reactor of zinc acetate, lowering mixed liquor with PH regulator at 30～40 DEG C is 5～6；
Step 2～4: reference example two preparation method step 2～4.
Comparative example five
Cold-box binder:
The preparation of component I: identical with embodiment four, the hydroxyl first of the high ortho position benzylic ether phenolic resin except for the difference that added
Base content is 25.98%.
The preparation of component II is with embodiment five.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain cold-box binder.
The preparation method of above-mentioned high ortho position benzylic ether phenolic resin refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 60 kilograms, paraformaldehyde 312 kilograms, zinc acetate 4 kilograms
Putting in reactor and stir, lowering mixed liquor with PH regulator at 30～40 DEG C is 5～6；
Step 2: with reference to comparative example three preparation method step 2～4.
Embodiment six
Cold-box binder:
The preparation of component I: equipped with in the mixing kettle of agitator, add the high ortho position benzylic ether phenolic aldehyde of high methylol group content
Resin 500 kilograms, dimethyl adipate 268 kilograms, 223 kilograms of Solvesso 100 aromatic hydrocarbons, 9 kilograms of A-187 silane, starts and stirs
Mix, mix about 2 hours, make material mix homogeneously.Wherein, the methylol group content of high ortho position benzylic ether phenolic resin is 36.39%,
Weight average molecular weight is 500.
The preparation of component II: equipped with in the mixing kettle of agitator, add polymethylene polyphenyl polyisocyanates 800,000
Gram, dioctyl adipate 151 kilograms, 40 kilograms of Solvesso 150 aromatic hydrocarbons, 9 kilograms of A-151 silane, starts stirring, mixes about 2
Hour, make material mix homogeneously.
With container, aforesaid liquid component I and liquid component II are packed respectively, i.e. obtain the cold-box binder of the present invention.
The cold-box binder of the present invention can be mixed with sand by the weight ratio of 0.55%～0.75% be applied to coloured
Casting, obtains non-ferrous casting molded body.
The preparation method of the high ortho position benzylic ether phenolic resin of above-mentioned high methylol group content refers to:
Step 1: by the phenol 420 kilograms melted, bisphenol-A 80 kilograms, paraformaldehyde 368 kilograms, calcium oxide 4 kilograms,
Stirring in 0.6 kilogram of input reactor of zinc acetate, lowering mixed liquor with PH regulator at 30～40 DEG C is 5～6；
Step 2: reference example three preparation method step 2～4.
Tackifying assistant in the embodiment of the present invention one to embodiment six includes that A187 silane etc. can omit, and omits thickening and helps
After agent, compared with the cold-box binder of the present invention not omitting tackifying assistant, the normal temperature strength of the resin sand after casting is almost
Do not change (intensity reduces within 2%).
Therefore, the present invention uses composite catalyst (calcium oxide and zinc acetate) technology to substantially increase high ortho position benzylic ether phenol
The methylol group content of urea formaldehyde, makes the methylol group content of high ortho position benzylic ether phenolic resin in the cold-box binder of the present invention
It is all higher than 27%.And the methylol group content of high ortho position benzylic ether phenolic resin prepared by the single catalyst of comparative example employing is less than
26%.
For proving that cold-box binder prepared by the present invention can improve the room temperature performance of resin sand, to resin sand further
Intensity is measured, and concrete grammar is with reference to GB2684 " Foundry sand and test mixture method ":
1) it is made into tree according to 100 weight portion great Lin normal sands, 0.3 parts by weight of component I, the ratio of 0.25 parts by weight of component II
Fat sand.Cold-box binder weight ratio in resin sand is 0.55%.
2) it is made into according to 100 weight portion great Lin normal sands, 0.34 parts by weight of component I, the ratio of 0.32 parts by weight of component II
Resin sand.Cold-box binder weight ratio in resin sand is 0.66%.
3) it is made into according to 100 weight portion great Lin normal sands, 0.39 parts by weight of component I, the ratio of 0.37 parts by weight of component II
Resin sand.Cold-box binder weight ratio in resin sand is 0.75%.
4) it is made into according to 100 weight portion great Lin normal sands, 0.45 parts by weight of component I, the ratio of 0.43 parts by weight of component II
Resin sand.Cold-box binder weight ratio in resin sand is 0.87%
The preparation method of resin sand: be firstly added component I and mix with normal sand 1 minute, adds component II and mixes 2 points
Clock, is then blown this resin sand by MLA1 core making machine and is pressed into transversetest core.Its core manufacturing craft parameter is: shooting pressure
0.3MPa, blows amine pressure 0.2Mpa, washs pressure 0.2Mpa, blows the amine time 3.0 seconds, wash time 5.0 seconds.
Measure 5 seconds initial bending strengths of transversetest core, 24 hours bending strength, 24 hours high wet strength (humidity respectively
>=95%).
Table 1 embodiment and the bending strength test of the made transversetest core of comparative example cold-box binder addition
By measuring 5 seconds of transversetest core initial bending strengths, 24 hours bending strengths, 24 hours high wet strengths respectively
(humidity >=95%) finds that the cold-box binder of the present invention can significantly improve bending resistance (pressure) intensity of resin sand, high humidity bending resistance
Intensity (moisture resistance).As shown in table 1, the cold-box binder to the embodiment of the present invention one to six is prepared resin sand transversetest core and is entered
Row test, found that the cold-box binder of the present invention is prepared by addition embodiment one to the embodiment six of 0.87%
The initial bending strength in 5 seconds of transversetest core is 2.38MPa～2.85MPa, and 24 hours bending strengths 3.98～4.42MPa, 24 is little
Time high humidity bending strength (>=95%) be 3.48MPa～3.91MPa；And the cold-box binder of comparative example is by the addition of 0.87%
5 seconds initial bending strengths of transversetest core of amount preparation are 1.35MPa～2.07MPa, 24 hours bending strengths 2.29MPa～
3.39MPa, 24 hours high humidity bending strength (>=95%) be 1.93MPa～2.89MPa.The cold-box binder of the present invention is described
Compare comparative example and can significantly improve its bending strength, the cold core of such as 0.87% embodiment one in the case of identical addition
24 hours bending strengths of the transversetest core of the addition of box binding agent are 4.26 ± 0.05MPa, and 24 hours of comparative example one resist
Curved intensity is 3.20 ± 0.06MPa, and its 24 hours bending strengths are described, i.e. room temperature bending resistance (pressure) intensity improves about 30%；Real
Executing example one 24 hours high humidity bending strength (>=95%) is 3.60 ± 0.05MPa, one 24 hours high humidity bending strengths of comparative example (>=
95%) it is 2.75 ± 0.06MPa, illustrates that bending resistance (pressure) intensity of its 24 hours high humidity bending strengths (>=95%), i.e. moisture-resisting carries
High by about 25%；And embodiment one is different (real from the methylol group content of comparative example one only high ortho position benzylic ether phenolic resin
Executing example one is 32.99%, and comparative example one is 25.38%), illustrate that the ortho position benzylic ether phenolic resin of high hydroxyl content can be significantly
Improve room temperature bending resistance (pressure) intensity of resin sand.
Measure the bending resistance of the transversetest core of the addition pressing 0.66%, 0.75%, 0.87% cold-box binder further
(pressure) intensity, is shown in Table 1.It is raw that research finds that the cold-box binder of the present invention only just can meet casting by the addition of 0.55%
Producing and need, 24 hours bending strengths of embodiment one to embodiment six can reach 2.79MPa～3.13MPa；0.66% cold core
24 hours bending strengths (room temperature bending strength) of the transversetest core of the addition of box binding agent are 3.01MPa～3.57MPa, with
24 hours bending strengths 2.29MPa of the addition of comparative example 0.87% cold-box binder～3.39MPa are close, such as,
24 hours bending strengths of the transversetest core of the addition of the cold-box binder of 0.66% embodiment one are 3.28 ±
0.06MPa, 24 hours bending strengths of the transversetest core of the addition of the cold-box binder of 0.87% comparative example one are 3.20
± 0.05MPa (is shown in Table 1.2), illustrates to reach identical resin sand bending strength, the addition of the cold-box binder of the present invention
Amount can reduce about 22% compared with comparative example；Embodiment five is compared with the cold-box binder of comparative example five simultaneously, except group
The methylol group content dividing the high ortho position benzylic ether phenolic resin in I is respectively 27.62% and 25.98%, and other components are the most identical,
Room temperature bending resistance (pressure) intensity (24 hours bending strengths) of its addition of 0.87% respectively 4.08 ± 0.05MPa and 3.39 ±
0.05MPa, its room temperature comprcssive strength also improves about 20%.Thus use the cold-box binder of the present invention to carry out non-ferrous metal
During casting, usage amount greatly reduces, and makes Resin-bonded sand mold and core mobility under pouring temperature increase, greatly improves resin bonded sand mould
The collapsibility problem of core, decreases the residual tar amount on metal die simultaneously, improves production efficiency.
The method using the present invention, the tar residual volume decreasing on metal die when carrying out sand core cast.Cast
The foundry goods of complicated shape, can pour into a mould more than 80 moulds continuously, and more than even 90 moulds, preferably state is more than 90 moulds.And it is traditional
Cold-box binder needs after pouring into a mould 10-30 mould continuously to clear up the tar on metal die.
With the resin of the present embodiment, industrialized production on aluminium head cast metal mould, each mulling of workshop mixing system
Capacity 200 kilograms, resin amount 0.65%, wherein component I is 55:45 with the ratio of component II, component I addition 0.715
Kilogram, component II addition 0.585 kilogram.
By the resin of comparative example, industrialized production on aluminium head cast metal mould, mixing system each mulling in workshop is held
Measuring 200 kilograms, resin amount 0.90%, wherein component I is 55:45 with the ratio of component II, and component I addition 0.99 is public
Jin, component II addition 0.81 kilogram.
The collapsibility method of testing of resin sand:
Take the room temperature placement sand sample test block of 24 hours to weigh (160 ± 1 grams), good with masking foil environmental sealing, put into constant temperature
The Muffle kiln roasting of 450 degree 15 minutes, takes out to put in 70 mesh vibrosieves after being cooled to room temperature and shakes 2 minutes, weigh residue
Sample weight.
By after sample weight after the weight of sample deducts roasting before roasting except weight before roasting, collapsibility carrys out table with percentage ratio
Show.
| Collapsibility % | |
| Embodiment 1 | 95% |
| Embodiment 2 | 90% |
| Embodiment 3 | 92% |
| Embodiment 4 | 96% |
| Embodiment 5 | 88% |
| Embodiment 6 | 92% |
| Comparative example 1 | 57% |
| Comparative example 2 | 52% |
| Comparative example 3 | 60% |
| Comparative example 4 | 56% |
| Comparative example 5 | 66% |
Therefore, the present invention leads to the high ortho position benzylic ether phenolic resin of the high methylol group using composite catalyst technology to prepare
Methylol group content is all higher than 27%, and the high ortho position benzylic ether phenolic resin that methylol group content is 32%～50% makes the present invention's
Cold-box binder effect is more excellent, makes the curing reaction efficiency of cold-box binder improve, the room temperature of resin is greatly improved
Performance, makes the normal temperature strength of resin sand improve about 30%, and moisture-resisting bending strength improves about 25%, and cold-box binder is ensureing
Under conditions of Resin-bonded sand mold and core intensity, addition is reduced to 0.55-0.75%, adds with the resin of prior art 0.85-1.2%
Amount is compared, and resin usage amount is substantially reduced, and makes Resin-bonded sand mold and core mobility under pouring temperature increase, greatly improves resin
The collapsibility problem of sand core, decreases the tar residual quantity on metal die simultaneously, improves production efficiency.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, it is also possible to make some improvements and modifications, these improvements and modifications are also
Should be regarded as protection scope of the present invention.
Claims (11)
1. a cold-box binder, including component I, it is characterised in that described component I is made up of the raw material of following weight portion:
Benzylic ether phenolic resin 40～80 parts
High boiling ester and/or hydrocarbon solvent 1～45 parts
Tackifying assistant 0～10 parts；
Wherein, the methylol group content of described benzylic ether phenolic resin is 32%～50%.
Cold-box binder the most according to claim 1, it is characterised in that also include component II, described component II by with
The raw material composition of lower weight portion:
Polyisocyanate 40～90 parts
High boiling ester and/or hydrocarbon solvent 5～45 parts
Tackifying assistant 0～10 parts.
Cold-box binder the most according to claim 1 and 2, it is characterised in that sense in described benzylic ether phenolic resin
Neighbour/the contrast of group is more than 1；It is highly preferred that described benzylic ether phenolic resin is that weight average molecular weight is at the high ortho position in 500～2000 benzyl
Ether phenolic resin.
4. according to the cold-box binder described in any one of claim 1-3, it is characterised in that in described component I and component II
High boiling ester and/or hydrocarbon solvent be each independently selected from as dibutyl phthalate, dioctyl phthalate, adjacent benzene two
Diisobutyl formate, diisooctyl phthalate, adipic acid dibutyl ester, dimethyl succinate, Glutaric Acid Dimethyl ester, adipic acid
One in the petroleum liquid aromatic hydrocarbons fraction of dimethyl ester, methanol, ethanol, butanol, isopropanol, boiling range 150～290 DEG C, kerosene
Or it is several；Wherein, the petroleum liquid aromatic hydrocarbons fraction of described boiling range 150～290 DEG C be solvesso 100, solvesso 150
Or one or more of solvesso 200.
5. according to the cold-box binder described in any one of claim 1-4, it is characterised in that in described component I and component II
Tackifying assistant be each independently selected from silane coupler, described silane coupler is A-187 silane, A-171 silane, A-172
One or more in silane, A-174 silane, A-151 silane.
6. according to the cold-box binder described in any one of claim 1-5, it is characterised in that described high ortho position benzylic ether phenolic aldehyde
Resin prepares by the following method:
Adding in reactor by aldehydes matter, aldehyde material, catalyst mixing, reaction prepares described phenolic resin；
The mol ratio of described aldehydes matter and aldehyde material is 1:1.0～1:3.0, preferably 1:1.2-1:2.5；
Catalyst is the catalyst system including slaine.
Cold-box binder the most according to claim 6, it is characterised in that described aldehydes matter is mixed phenol；Preferably,
One or both the combination in phenol, alkyl phenol of the described phenol mixture；Preferably, described alkyl phenol is selected from 2,6-bis-
Methylphenol, orthoresol, metacresol, paracresol, 3,5-xylenol, 3,4-xylenol, 3-ethyl phenol, 3,5-diethyl
Base phenol and the combination of one or more to butylphenol.
8. according to the cold-box binder described in claim 6 or 7, it is characterised in that described in include the catalyst of slaine
System is for comprising zinc salt and lead salt；Preferably, the catalyst system of slaine is included described in for comprising zinc salt；It is furthermore preferred that
Described zinc salt is one or more in zinc acetate, zinc sulfate, zinc chloride, zinc naphthenate.
9. according to the cold-box binder described in any one of claim 2-8, it is characterised in that the poly-isocyanide in described component II
Acid esters is selected from diphenyl methane-4,4 '-diisocyanate, thick diphenyl methane-4,4 '-diisocyanate or the many benzene of polymethylene
One or more in Quito carbimide, hexamethylene diisocyanate, isophorone diisocyanate.
10. a casting body, it is characterised in that arbitrary described cold by casting aggregate and claim 3-9 of effective dose
Prepare under catalyst action after the mixing of core box binding agent；Wherein, by described component I and the group of described cold-box binder
Point II is sequentially added into, or is simultaneously introduced and mixes with described casting aggregate.
11. casting bodies according to claim 10, it is characterised in that described cold-box binder by 0.55%～
The weight ratio of 0.75% mixes with described casting aggregate.
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| CN112059103B (en) * | 2020-08-31 | 2021-09-24 | 安徽省含山县威建铸造厂(普通合伙) | Preparation method and application of acid-process cold core box resin for casting |
| CN112548023A (en) * | 2020-12-08 | 2021-03-26 | 四川东树新材料有限公司 | Cold core box resin for high-collapsibility cast aluminum engine cylinder body and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106040966B (en) | 2019-02-05 |
| WO2017173859A1 (en) | 2017-10-12 |
| CN106046283B (en) | 2019-04-09 |
| CN106046283A (en) | 2016-10-26 |
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